CN101560365A - Coating-type binder used for bonding natural rubber and metallic framework and preparation method - Google Patents
Coating-type binder used for bonding natural rubber and metallic framework and preparation method Download PDFInfo
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Abstract
The invention provides a coating-type binder used for bonding natural rubber and a metallic framework and a preparation method. The coating-type binder is prepared from a composite binder, rubber and an auxiliary agent, wherein the composite binder consists of cobalt boracyl 23 and cobalt neocaprate, the rubber is natural rubber, the auxiliary agent consists of an age resister, a plasticizer, a filling agent, a strengthening agent, an accelerator, an activator, a silane coupling agent and a vulcanizing agent which are of conventional use in rubber product production. The composite binder is dispersed in rubber material and coordinates with the age resister, the plasticizer, the filling agent, the strengthening agent, the accelerator, the activator, the silane coupling agent and the vulcanizing agent to form a bonding master batch, and the bonding master batch is dissolved by solvent of oil to prepare a mucilage, thus the coating-type binder used for bonding natural rubber and metallic framework is obtained. The coating-type binder used for bonding natural rubber and metallic framework can be used in middle-size and small-size rubber product industry, and can also be used on the refurbishment of radial ply tires of steel wires and the production of rubber products such as steel wire reinforcement traveling belt joint glue filling.
Description
Technical field
The present invention relates to tamanori, be meant that especially a kind of natural rubber that is used for comprises the mixed rubber of natural rubber and general purpose synthetic rubber and natural rubber and metallic framework coating-type binder used for bounding and the preparation method that copper, zinc, copper alloy, zinc alloy, aluminum alloy framework bind usefulness.
Background technology
When existing natural rubber goods relate to natural rubber and apply bonding with the mixed rubber of general purpose synthetic rubber with copper, zinc, copper alloy, zinc alloy, aluminum alloy framework material, the bonding method mainly adopts the import coating-type binder based on the physics bonding, because this type of tamanori exists the defective of ageing-resistant particularly heat-proof aging and hydrothermal aging and dynamic properties difference, can not satisfy the production needs of present natural rubber goods.At present, strengthen the large-scale rubber item industry that serializations such as travelling belt, wire braided hose are produced at radial wire cord tire, steel wire, the elastomerics such as rubber and the high strength of zinc-plated, that the brass-plated steel wire cord is woven into framework material are binded the direct addition type cobalt salt tamanori of employing usually.As organic acid cobalt salt such as adding cobalt naphthenate, cobalt stearate, cobalt oleate, cobaltous linoleate, citronellic acid cobalt, toxilic acid cobalt as described in the Chinese patent CN200410001668.4.Along with science and technology development, from the eighties in last century, various high performance direct addition type cobalt salt tamanoris come out successively, and wherein performance is the most superior cobalt boracylate (external trade mark Manobond680C) and new cobalt decanoate (Manobond740C).Though the production that these cobalt salt tamanoris are applied to the Large Scale and Continuous rubber item has obtained effect preferably, but be not suitable for middle-size and small-size rubber item, protect string, bearing, sealing member, sebific duct etc. as rubber absorbers, rubber, these product surface shapes are special, the single-piece glue consumption is little and adopt the batch production mode usually, but generally adopt coating rubber-metal-to-metal adhesive.And directly addition type cobalt salt tamanori can only be applicable to the high strength bonding of rubber and brass-plating, galvanized steel wire cord, and is not suitable for copper, zinc and alloy thereof that middle-size and small-size rubber item generally adopts and the bonding of aluminum alloy framework material.At present, but middle-size and small-size rubber item industry is used coating rubber-metal-to-metal adhesive usually, but and the main dependence on import of coating rubber-metal-to-metal adhesive.This class organic type mixture tamanori belongs to the heat vulcanization type tamanori, under cure conditions, the bonding of rubber and metal mainly rely on resin to the infiltration of metallic surface, adsorb and adhere to; Because the bonding process of rubber and metal belongs to physical process, no chemical reaction takes place, and this has just determined the cement properties of this class tamanori poor, heat aging performance is poor, dynamic properties is poor.From using the result, easily come unstuck in the use of adherent goods; Because the use of this class tamanori generally all is divided into primer and face glue, needs twice coating during use, thereby bind troublesome poeration; And this class tamanori price is more expensive relatively, the use cost height; Also because the organic composition complexity in this class tamanori, need to adopt the mixed solvent of forming by aromatic hydrocarbon ester class, ketone to dissolve and dilute, poisonous owing to mixed solvent, harmful, cause in production and the use and can have a strong impact on industrial hygiene and contaminate environment.
Summary of the invention
Technical problem to be solved by this invention just is not to be suitable for coating production technique production and with framework material higher requirement to be arranged to binding at existing cobalt salt tamanori, but and at present coating rubber-metal-to-metal adhesive to exist ageing-resistant particularly heat aging property poor, the use cost height, bind the situation of complicated operation trouble and tamanori solvent contamination environment, providing a kind of serves as that the basis applies natural rubber and metallic framework coating-type binder used for bounding and preparation method that production technique is produced with two kinds of compound natural rubber goods that are applicable to that carry out the modification processing of single cobalt salt tamanori with direct addition type cobalt salt tamanori.
Natural rubber of the present invention and metallic framework coating-type binder used for bounding are prepared from by composite adhesive and rubber and auxiliary agent, composite adhesive is made of cobalt boracylate 23 and new cobalt decanoate, rubber is natural rubber, and auxiliary agent comprises conventional anti-aging agent, softening agent, weighting agent, strengthening agent, promotor, promoting agent, silane coupling agent and the vulcanizing agent that uses of rubber item production; Be scattered in the rubber raw materials and cooperate anti-aging agent, softening agent, weighting agent, strengthening agent, promotor, promoting agent, silane coupling agent and vulcanizing agent to form by composite adhesive and bind rubber master batch; Make rubber cement by industrial naptha dissolving bonding rubber master batch and obtain natural rubber and metallic framework coating-type binder used for bounding; The constituent mass per distribution ratio of natural rubber and metallic framework coating-type binder used for bounding is:
(1): composite adhesive:
In the composite adhesive quality is 100%, and cobalt boracylate 23 is 45-65%, and new cobalt decanoate is 35-55%;
(2) bind rubber master batch:
To bind the rubber master batch quality is 100%, natural rubber 35-60%, composite adhesive 1.5-5%, anti-aging agent 1.5-4%, softening agent 2-6%, weighting agent 0-20%, strengthening agent 20-35%, promotor 0.5-2.5%, promoting agent 2-4%, silane coupling agent 0.2-1%, vulcanizing agent 1.5-4%.
(3) rubber cement:
In the rubber cement quality is 100%, and binding rubber master batch B is 20%, and industrial naptha is 80%.
The best in quality per distribution ratio of natural rubber and metallic framework coating-type binder used for bounding component is:
(1) composite adhesive:
In composite adhesive is 100%, and cobalt boracylate 23 is 53%, and new cobalt decanoate is 47%;
(2) bind rubber master batch:
To bind rubber master batch is 100%, and natural rubber 48.31%, composite adhesive 2.42%, anti-aging agent 4020 are 0.97%, anti-aging agent RD is 0.97%; Softening agent coumarone 0.97%, Stockholm tar 4.83%, the white carbon black 4.83% of strengthening agent, semi-reinforcing carbon black SRF are 19.32%, weighting agent lime carbonate 9.66%, accelerant N OBS are 1.21%, promoting agent zinc oxide 2.89%, stearic acid 0.72%; Silane coupling agent 0.48%, vulcanizing agent sulphur 2.42%.
(3) rubber cement:
In the rubber cement quality is 100%, and binding rubber master batch B is 20%, and industrial naptha is 80%.
Natural rubber of the present invention and each component raw material of metallic framework coating-type binder used for bounding are selected industrial raw material for use.It is raw material that composite adhesive adopts cobalt boracylate 23 and new cobalt decanoate, and the molecular formula of cobalt boracylate 23 is: B (OCoR)
3, R is the mixing acid group of neodecanoic acid, PIVALIC ACID CRUDE (25), propionic acid in the formula, molecular-weight average is 600-620; Main physical and chemical indexes is: cobalt contents is 22.5 ± 0.5%, and fusing point 110-125 ℃, heptane insolubles is less than 0.5%, the qualitative examination boracic.The molecular formula of new cobalt decanoate is: CoR
2, R is the mixing acid group of neodecanoic acid, PIVALIC ACID CRUDE (25), propionic acid in the formula, molecular-weight average is 285-290; Physical and chemical indexes is: cobalt contents 20.5 ± 0.5%, softening temperature 80--100 ℃.Natural rubber adopts the 1# rubber smoked sheet.Anti-aging agent, softening agent, strengthening agent, weighting agent, promotor, promoting agent, silane coupling agent and vulcanizing agent adopt normally used auxiliary agent in the rubber item production.For example anti-aging agent can be selected acetone and pentanoic pyrocondensation thing (BLE), acetone and pentanoic pyrocondensation thing+lime carbonate (BLE-C), N-sec.-propyl-N-diphenyl-para-phenylene diamine (4010NA), (1, the 3-dimethylbutyl)-N-diphenyl-para-phenylene diamine (4020) etc. for use; Softening agent can be selected coumarone indene resin, dibutyl phthalate for use; Strengthening agent can be selected carbon black, white carbon black, ferric oxide etc. for use, but white carbon black need be through silane coupling agent surface treatment use, and weighting agent adopts light calcium carbonate usually; Promotor can be selected N one tertiary butyl one 2 one benzothiazole sulphenamides (NS), ziram (S), vulkacit D (DPG) etc. for use; Promoting agent adopts zinc oxide, magnesium oxide, weisspiessglanz etc.; Silane coupling agent adopts two (three ethoxy stem silane propyl group) tetrasulfides usually, and the silane coupling agent trade mark commonly used is KH-845-4; Vulcanizing agent can be selected common sulphur or insoluble sulfur for use, also can use dithio morpholine.
The raw materials quality technical requirements of natural rubber of the present invention and metallic framework coating-type binder used for bounding is listed in the table below.
Natural rubber and metallic framework coating-type binder used for bounding raw materials for production technical indicator
| Sequence number | Material name | Index |
| 1 | Cobalt boracylate 23 | Cobalt contents 22.5 ± 0.5%; Heptane insolubles≤0.5% |
| 2 | New cobalt decanoate | Cobalt contents 20.5 ± 0.5%; Softening temperature 80-100 ℃ |
| 3 | Rubber | Natural gum is the 1# rubber smoked sheet. |
| 4 | Vulcanizing agent | Select insoluble sulfur 8010 for use; Sulphur content 90.0 ± 1.0% |
| 5 | Promoting agent | Zinc oxide, particle diameter≤200 orders |
| 6 | Weighting agent | Light calcium carbonate |
| 7 | Silane coupling agent | KH-845-4 |
| 8 | Anti-aging agent | Conventional |
| 9 | Strengthening agent | Conventional |
| 10 | Softening agent | Conventional |
| 11 | Promotor | Conventional |
The preparation of natural rubber of the present invention and metallic framework coating-type binder used for bounding is divided into composite adhesive preparation, bind rubber master batch preparation and rubber cement prepares three steps and carries out, and preparation flow is as follows:
The first step:
Second step:
The 3rd step:
Preparation process major control condition:
(1) composite adhesive preparation: 120 ℃ of new cobalt decanoate fusion controlled temperature add cobalt boracylate 23 control intensification temperature to 180 ℃ formation homogeneous liquation in the time of 120 ℃; Homogeneous liquation cooling temperature normal temperature;
(2) bind the rubber master batch preparation: natural gum is plasticated in mill, plasticates roller Wen Wendu＜50 ℃ time 8-10 minute, broken-(down)rubber and composite adhesive and auxiliary agent in mill mixing time 15-20 minute, parked 16-24 hour roller Wen Wendu＜60 ℃, and it is standby to roll into the 4-6mm thin slice;
(3) rubber cement preparation: shear and bind rubber master batch particle≤1cm * 1cm, stir 50 rev/mins of the mixing speed that slurry is sheared dissolving slurrying, the dissolving terminal point is that 99% rubber cement filters by 200 eye mesh screens.
When carrying out the preparation of natural rubber and metallic framework coating-type binder used for bounding; the first step is carried out the composite adhesive preparation earlier; with quantitative new cobalt decanoate in container in 120 ℃ of fusions; form in " molten bath "; progressively add quantitative cobalt boracylate 23 in " molten bath " then; be warming up to 180 ℃, it is standby after cooling off that formation homogeneous liquid state goes out to put granulation.The intermediate product composite adhesive of preparation reaches following technical indicator: cobalt contents 21.5 ± 0.5%, softening temperature 80-100 ℃.Second step was binded the rubber master batch preparation, the natural rubber of calculated amount is plasticated in mill, plasticated time 8-10 minute, roller Wen Wendu＜50 ℃, again with broken-(down)rubber and composite adhesive and auxiliary agent at mill mixing, mixing time 15-20 minute, roller Wen Wendu＜60 ℃, roll into sheet and parked 16-24 hour, it is standby to roll into the 4-6mm thin slice then in mill.The 3rd step was carried out the rubber cement preparation, standby bonding rubber master batch shearing of thin disc is broken into the little granular particle of 1cm * 1cm, add then and can dissolve the industrial naptha immersion of binding rubber master batch and shear dissolving, make rubber cement, after 18 hours, take a sample to check, slurries can be the dissolving terminal point by 200 eye mesh screens more than 99%, and the slurries that dissolving is good obtain application type modification cobalt salt tamanori product after 200 mesh sieves filter.Slurries should meet following index: density: 0.82 ± 0.05mg/ml, solid content: 20 ± 1%.The industrial naptha that binds the rubber master batch solvent as dissolving is 120# or 200# straight chain hydrocarbon industrial naptha.Natural rubber of the present invention and metallic framework coating-type binder used for bounding are rubber cement shape product, abundant mixing during use according to the using method difference, is used to brush that then rubber cement is denseer, spray then rarelyr, can add with kind solvent tamanori and dilute so that help operation.Tamanori sprayed or brushing or roller coat behind the metallic framework surface, volatilization is solvent to the greatest extent, again with rubber and metal pressing, in vulcanizer or vulcanizing boiler, cure conditions by rubber item vulcanizes, and general temperature is 100-180 ℃, and pressure is 0.5-10MPa, time is 5min-2h, can obtain high-intensity cement properties.The quality and technical index such as the following table of natural rubber of the present invention and metallic framework coating-type binder used for bounding finished product:
The quality and technical index of natural rubber and metallic framework coating-type binder used for bounding finished product
| Sequence number | Title | Index |
| 1 | Viscosity (be coated with-4 and measure 20 ℃ in cup) | 17-19min |
| 2 | Solid content | 20±1％ |
| 3 | Density | 0.82±0.05mg/ml |
| 4 | Coated area (when build is 15 μ) | 12-15m 2/kg |
Advantage of the present invention just is because the tamanori component has adopted the two kinds of direct addition type cobalt salt of high level tamanori raw materials can having complementary advantages, make the tamanori use-pattern become application type by modification, satisfied the needs of rubber item processing by direct addition type; Tamanori after the modification had both kept various excellent properties such as the high strength bonding of former direct addition type cobalt salt tamanori, anti-aging, heat-resisting oxygen, moisture-proof heat, salt water resistance corrosion, simultaneously can apply use as import applies the tamanori product again, result of use is obvious.And the cobalt salt tamanori after the modification goes for the bonding of multiple metallic frameworks such as natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber and mixed rubber thereof and brass-plating, zinc-plated, copper, zinc, copper alloy, zinc alloy, aluminium alloy.Natural rubber of the present invention and metallic framework coating-type binder used for bounding have Heat stability is good, and dynamic properties is good; The advantage that price is lower is compared with the import series product, and the user can reduce use cost about 50%.Solvent for use is nontoxic substantially straight chain hydrocarbon industrial naptha, helps protecting environment and industrial hygiene.Natural rubber of the present invention and metallic framework coating-type binder used for bounding both can be used for middle-size and small-size rubber item industry, also can be used for the radial wire cord tire renovation, and steel wire strengthens the production that the travelling belt joint is mended rubber items such as glue.Thereby natural rubber of the present invention and metallic framework coating-type binder used for bounding have good popularization and application prospect.
Embodiment
Below be embodiments of the invention, the actual use of the present invention is not limited to embodiment.
Embodiment 1, natural rubber and metallic framework coating-type binder used for bounding and preparation method
(1) starting material
| The starting material title | Specification index, the trade mark | Production unit |
| Cobalt boracylate | Cobalt contents 22.5 ± 0.5%; Heptane insolubles≤0.5% | Zhenjiang steps special |
| New cobalt decanoate | Cobalt contents 20.5 ± 0.5%; Softening temperature 80-100 ℃ | Zhenjiang steps special |
| Natural rubber | The 1# rubber smoked sheet | Yunnan |
| Coumarone | Accord with Q 02ZLH005-1999 | The Qingdao sharp chemical industry that shakes |
| Stockholm tar | Conventional | Qingdao gets intelligent chemical industry |
| Anti-aging agent 4020 | Meet (HG/T 3644-1999) | The chemical plant, Nanjing |
| Anti-aging agent RD | Meet GB 8826-2003 | Zibo three good fortune chemical industry |
| Antioxidant BLE | Meet HG2-1482-83 | The auxiliary reagent factory, Qingdao |
| White carbon black | The special use of QS-15 type tamanori | Shanghai Xi Meng chemical industry |
| High abrasion carbon black N220 | Conventional | Yixing carbon plant |
| Semi-reinforcing carbon black SRF | Conventional | Yixing carbon plant |
| Accelerant N OBS | Meet GB8829-88 | Rongcheng, Shandong chemical industry |
| Vulkacit D | Meet HG2342-92 | Yongjia, Zhejiang chemical industry |
| Accelerator NS | Meet (HG/T2744-1996) | Yongjia, Zhejiang chemical industry |
| Composite adhesive | Cobalt contents 21.5±0。5% softening temperature 80-100 ℃ | Self-control |
| Active zinc flower | Meet the special-purpose A level of HHXPQB-YHX (XJ)-2005 high-grade rubber | Yue Dong chemical plant, Shanghai |
| Light calcium carbonate | Meet HG/T2226-2000 | Sky, Yixing power chemical industry |
| Silane coupling agent | Conventional | Nanjing dawn chemical industry |
| Stearic acid | Meet GB9103-88Y-4 | Ten thousand friendly chemical plant, Zibo |
| Sulphur | Meet HG/T2525-93 | The precious Longhua worker in Henan |
(2) production unit
| Device name | Specifications and models | Quantity | The manufacturer |
| Two roller mills | XK-400 | 1 | Dalian China Korea Spro rubber industry company |
| Shears | TH-7006 | 1 | Sky, Jiangdu favour test machines company |
| Change-can mixer | XB-1000 | 10 | Wolong, Jiangyin City rubber and plastics machine factory |
| Rotate through screen | Diameter phi 600mm crosses grit number 200 orders | 10 | Wuxi medicine instrument factory |
| Mixing tank | Diameter * highly=φ 700mm * h1200mm | 10 | Wuxi medicine instrument factory |
| Stainless steel cauldron | V＝1m 3, electrothermic type | 2 | Wuxi medicine instrument factory |
(3) set of dispense ratio
Table 1 composite adhesive proportioning table (is 100% in the composite adhesive quality)
Illustrate: preparation weight is the 100KG meter.
Table 2 binds rubber master batch proportioning table (quality in the bonding rubber master batch is 100%)
Illustrate: I in this table.II。In the employed composite adhesive difference correspondence table 1 of filling a prescription for III number.I。II。III number prescription.
It is 50KG that the bonding rubber master batch once prepares weight
(4) preparation process major control condition:
(1) composite adhesive preparation: 120 ℃ of new cobalt decanoate fusion controlled temperature add cobalt boracylate 23 control intensification temperature to 180 ℃ formation homogeneous liquation in the time of 120 ℃; Homogeneous liquation cooling temperature normal temperature;
(2) bind the rubber master batch preparation: natural gum is plasticated in mill, plasticates roller Wen Wendu＜50 ℃ time 8-10 minute, broken-(down)rubber and composite adhesive and auxiliary agent in mill mixing time 15-20 minute, parked 16-24 hour roller Wen Wendu＜60 ℃, and it is standby to roll into the 4-6mm thin slice;
(3) rubber cement preparation: shear and bind rubber master batch B particle≤1cm * 1cm, stir 50 rev/mins of the mixing speed that slurry is sheared dissolving slurrying, the dissolving terminal point is that 99% rubber cement filters by 200 eye mesh screens.
When carrying out the preparation of natural rubber and metallic framework coating-type binder used for bounding, the first step is carried out composite adhesive preparation earlier, with quantitative new cobalt decanoate at 1M
3In 120 ℃ of fusions, form " molten bath " in the stainless steel cauldron, then quantitative cobalt boracylate 23 is progressively added in " molten bath ", be warming up to 180 ℃, formation homogeneous liquid state, the homogeneous liquation goes out to put granulation and is cooled to behind the normal temperature standby.The intermediate product composite adhesive of preparation reaches following technical indicator:: cobalt contents 21.5 ± 0.5%, softening temperature 80-100 ℃.Second step was binded the rubber master batch preparation, the natural rubber of calculated amount is plasticated in mill, plasticated time 8-10 minute, roller Wen Wendu＜50 ℃, then with broken-(down)rubber and composite adhesive and auxiliary agent at mill mixing, mixing time 15-20 minute, roller Wen Wendu＜60 ℃, roll into sheet and parked 16-24 hour, it is standby to roll into the 4-6mm thin slice again in mill.The 3rd step was carried out the rubber cement preparation, standby bonding rubber master batch shearing of thin disc is broken into the little granular particle of 1cm * 1cm, to bind the rubber master batch particle then puts into the XB-1000 change-can mixer and can dissolve the 120# straight chain hydrocarbon industrial naptha immersion of binding rubber master batch according to the ratio adding of quality 20%: 80%, make rubber cement through the industrial naptha immersion and by change-can mixer shearing dissolving, after 18 hours, take a sample to check, slurries can be the dissolving terminal point by 200 eye mesh screens more than 99%, dissolving slurries well are by after rotating through the screen filtration, enter into mixing tank, the solvent of adding according to calculated amount is also by change-can mixer, filter sieve enters into mixing tank, abundant mixing obtains natural rubber and metallic framework coating-type binder used for bounding product in mixing tank.Slurries should meet following index: density: 0.82 ± 0.05mg/ml, solid content: 20 ± 1%.
The quality and technical index of natural rubber and metallic framework coating-type binder used for bounding finished product
| Sequence number | Title | Index |
| 1 | Viscosity (be coated with-4 and measure 20 ℃ in cup) | 17-19min |
| 2 | Solid content | 20±1％ |
| 3 | Density | 0.82±0.05mg/ml |
| 4 | Coated area (when build is 15 μ) | 12-15m 2/kg |
To the theoretical investigation of cobalt salt tamanori, at present prevailing is catalytic theory, can be set forth the adhesion mechanism of natural rubber of the present invention and metallic framework coating-type binder used for bounding by catalytic theory according to both at home and abroad.The cobalt salt tamanori is under (100-200 ℃) condition of being heated, and cracking discharges the active cobalt ion, under the catalysis of active cobalt ionic, and metal and sulphur generation chemical reactions such as copper, zinc, generation can not as copper, generate Cu with stoichiometric metallic sulfide
2S
x, its reaction equation is:
2Cu+XS＝Cu
2S
x
Cu
2S
xIn the S atom the other end then enter on the net structure node of rubber, just at metal and rubber intermediate formation " sulphur bridge ", sulphur and metal be combined into ionic linkage, the bond energy of ionic linkage is at 586-1047KJ/moL; The combination of combination between the sulphur atom and sulphur and rubber is covalent linkage, and the bond energy of covalent linkage is 63-712KJ/moL, and this just makes rubber and metal carry out the high-tenacity bonding by chemical bond fully.The mixing by a certain percentage of cobalt boracylate and new cobalt decanoate is used; both made rubber cement of the present invention keep the excellent properties of direct addition type cobalt salt tamanori; make the stringent process conditions of the single cobalt boracylate of former use become loose and stable again, the different technology conditions of the different rubber item of easier adaptation producer.Because the bonding of rubber and metal is to finish by the bonding of chemical bond fully, the bond energy of this chemical bond is big, Heat stability is good, this has just determined tamanori of the present invention being far superior to other main physics adherent rubber-metal tamanori that relies between rubber and metal aspect thermotolerance and the dynamic properties.In direct addition type cobalt salt cracking process, except that discharging the active cobalt ion, discharge the boron acyl group simultaneously, the boron acyl group has two sexual functions, can in and the bronsted lowry acids and bases bronsted lowry in the goods, therefore, make goods that wet and heat ageing resistant and salt water resistance aging resistance preferably be arranged; Simultaneously, the boron acyl group also has good flame retardancy.In sum, be exactly the principle place that tamanori of the present invention can keep and expand the high strength cement properties of former direct addition type cobalt salt tamanori and anti-aging, heat-resisting oxygen, moisture-proof heat, salt water resistance corrosive property.
Compare with present widely used application type rubber-metal tamanori, tamanori of the present invention has following advantage: (1) has similar high strength to bind ability; (2) have better ageing-resistant performance, particularly heat-proof aging and salt water resistance corrosive nature; (3) broad spectrum is good, as long as different with framework material according to the glue kind, adopts the rubber cement of the present invention of the different trades mark, tens trades mark that can import substitutes; (4) the rubber-metal tamanori that uses at present is divided into primer, face glue usually, needs earlier during use coat primer in the metallic surface, treat that its solvent evaporates to the greatest extent after, be coated with top glue again, treat that again solvent evaporates to the greatest extent after, just can carry out hot sulfurization and bind.Rubber cement of the present invention only needs primary coating, treat that solvent evaporates to the greatest extent after, can carry out hot sulfurization and bind, make operation greatly easy; (5) form by multiple organism because of the rubber-metal tamanori that uses at present, in order to adapt to multiple organic dissolution characteristics, usually all to adopt the mixed solvent of forming by aromatic hydrocarbon, ester class, ketone to dissolve and dilute, poisonous owing to solvent, harmful, had a strong impact on industrial hygiene and contaminate environment.Rubber cement solvent of the present invention is common direct steel hydrocarbon 120# or 200# solvent oil, and is nontoxic substantially, harmless, and cheap.(6) the commercially available price of rubber cement of the present invention is about 60% of a similar imported product, adds the factor of the cheap and per kilogram rubber cement coated area of solvent greater than imported product 30%, 50% of user's the not enough similar imported product of actual use cost.
According to formula I, formula I I, formula I II rubber cement of the present invention is respectively applied for natural gum, the epoxy glue of natural gum and butadiene-styrene rubber, the naked Steel Skeleton material of the epoxy glue of natural gum and butadiene-styrene rubber, cis-butadiene cement and carbon steel adherent cement properties and aging resistance are listed as following table:
Three assembly side's cement properties and aging resistance comparison sheet
| Cement properties (extraction power/N) | Formula I | Formula I I | Formula I II |
| Before aging | 590 | 590 | 590 |
| After the thermal ageing | 440 | 460 | 470 |
| After the steam aging | 540 | 540 | 560 |
| After moisture is aging | 520 | 530 | 540 |
| After salt solution is aging | 520 | 540 | 550 |
From form listed cement properties and aging resistance data: three assembly Fang Jun have good initial adhesive power and ageing resistance.Data have fully been reacted tamanori of the present invention and have been had good heat-resistant and thermal stability, and according to the application result of user feedback, tamanori of the present invention also has good dynamic properties.The selling price that tamanori of the present invention is adjusted is 7.0 ten thousand yuan/ton, is regardless of primer and face glue during use, only needs primary coating.And external similar imported product is divided into primer and face glue, need coat primer earlier during use, treats to be coated with top glue again after solvent evaporates to the greatest extent, treats just can bind after solvent evaporates to the greatest extent again; The price of external product primer is 150,000 yuan/ton at present, and the price of face glue is 120,000 yuan/ton.The used thinner of tamanori of the present invention is nontoxic substantially 120# solvent oil, price only is 6000 yuan/ton, and the used thinner of similar imported product is the mixed diluent that contains organic solvents such as benzene class, ketone, ester class, price is about 30,000 yuan one ton, and toxicity and smell are all bigger.Therefore, compare with the import like product, 50% of the not enough imported product of the use cost of tamanori of the present invention, and help the industrial hygiene of environment protection and operationlocation.
Claims (10)
1, a kind of natural rubber and metallic framework coating-type binder used for bounding, it is characterized in that being prepared from by composite adhesive and rubber and auxiliary agent, composite adhesive is made of cobalt boracylate 23 and new cobalt decanoate, rubber is natural rubber, and auxiliary agent comprises conventional anti-aging agent, softening agent, weighting agent, strengthening agent, promotor, promoting agent, silane coupling agent and the vulcanizing agent that uses of rubber item production; Be scattered in the rubber raw materials and cooperate anti-aging agent, softening agent, weighting agent, strengthening agent, promotor, promoting agent, silane coupling agent and vulcanizing agent to form by composite adhesive and bind rubber master batch; Make rubber cement by industrial naptha dissolving bonding rubber master batch and obtain natural rubber and metallic framework coating-type binder used for bounding; The constituent mass per distribution ratio of natural rubber and metallic framework coating-type binder used for bounding is:
(1): composite adhesive: in the composite adhesive quality is 100%, and cobalt boracylate 23 is 45-65%, and new cobalt decanoate is 35-55%;
(2) bind rubber master batch: to bind the rubber master batch quality is 100%, natural rubber 35-60%, composite adhesive 1.5-5%, anti-aging agent 1.5-4%, softening agent 2-6%, weighting agent 0-20%, strengthening agent 20-35%, promotor 0.5-2.5%, promoting agent 2-4%, silane coupling agent 0.2-1%, vulcanizing agent 1.5-4%.
(3) rubber cement: in the rubber cement quality is 100%, and binding rubber master batch B is 20%, and industrial naptha is 80%.
2, natural rubber according to claim 1 and metallic framework coating-type binder used for bounding, the molecular-weight average that it is characterized in that cobalt boracylate 23 is 600-620, and cobalt contents is 22.5 ± 0.5%, fusing point 110-125 ℃, heptane insolubles is less than 0.5%, the qualitative examination boracic; The molecular-weight average of new cobalt decanoate is 285-290, cobalt contents 20.5 ± 0.5%, softening temperature 80--100 ℃.
3, natural rubber according to claim 1 and metallic framework coating-type binder used for bounding is characterized in that natural rubber is the 1# rubber smoked sheet.
4, natural rubber according to claim 1 and 2 and metallic framework coating-type binder used for bounding is characterized in that the constituent mass per distribution ratio of tamanori is:
(1) composite adhesive: in composite adhesive is 100%, and cobalt boracylate 23 is 53%, and new cobalt decanoate is 47%;
(2) bind rubber master batch: to bind rubber master batch is 100%, and natural rubber 48.31%, composite adhesive 2.42%, anti-aging agent 4020 are 0.97%, anti-aging agent RD is 0.97%; Softening agent coumarone 0.97%, Stockholm tar 4.83%, the white carbon black 4.83% of strengthening agent, semi-reinforcing carbon black SRF are 19.32%, weighting agent lime carbonate 9.66%, accelerant N OBS are 1.21%, promoting agent zinc oxide 2.89%, stearic acid 0.72%; Silane coupling agent 0.48%, vulcanizing agent sulphur 2.42%.
5, natural rubber according to claim 1 and 2 and metallic framework coating-type binder used for bounding is characterized in that the constituent mass per distribution ratio of tamanori is:
(1) composite adhesive: in composite adhesive is 100%, and cobalt boracylate 23 is 62%, and new cobalt decanoate is 38%;
(2) bind rubber master batch: to bind rubber master batch is 100%, natural rubber 57.01%, composite adhesive 3.42%, antioxidant BLE is 2.28%, softening agent coumarone 2.28%, and the white carbon black 6.85% of strengthening agent, semi-reinforcing carbon black SRF are 19.95%, vulkacit D is 0.12%, accelerator NS is 0.57%, promoting agent zinc oxide 2.85%, stearic acid 0.57%, silane coupling agent 0.68%, vulcanizing agent sulphur 3.42%.
6, natural rubber according to claim 1 and 2 and metallic framework coating-type binder used for bounding is characterized in that the constituent mass per distribution ratio of tamanori is:
(1) composite adhesive: in composite adhesive is 100%, and cobalt boracylate 23 is 48%, and new cobalt decanoate is 52%;
(2) bind rubber master batch: to bind rubber master batch is 100%, natural rubber 38.10%, composite adhesive 1.52%, anti-aging agent 4020 is 0.76%, anti-aging agent RD is 0.76%, antioxidant BLE is 0.76%, softening agent coumarone 0.76%, Stockholm tar 3.81%, the white carbon black 3.81% of strengthening agent, high abrasion carbon black N220 is 7.62%, semi-reinforcing carbon black SRF is 17.14%, weighting agent lime carbonate 19.05%, accelerant N OBS is 0.95%, accelerator NS is 0.19%, promoting agent zinc oxide 1.91%, stearic acid 0.57%, silane coupling agent 0.38%, vulcanizing agent 1.91%.
7, natural rubber according to claim 1 and 2 and metallic framework coating-type binder used for bounding, being coated with-4 when it is characterized in that 20 ℃ of natural rubber and metallic framework coating-type binder used for bounding finished products, to measure glass viscosity be 17-19min, solid content is 20 ± 1%, density is 0.82 ± 0.05mg/ml, and coated area was 12-15m when build was 15 μ
2/ kg.
8, natural rubber according to claim 1 and metallic framework coating-type binder used for bounding is characterized in that the industrial naptha as dissolving bonding rubber master batch solvent is a 120# straight chain hydrocarbon industrial naptha.
9, natural rubber according to claim 1 and metallic framework coating-type binder used for bounding is characterized in that the industrial naptha as dissolving bonding rubber master batch solvent is a 200# straight chain hydrocarbon industrial naptha.
10, the preparation method of a kind of natural rubber and metallic framework coating-type binder used for bounding is characterized in that preparation process is divided into composite adhesive preparation, binds rubber master batch preparation and rubber cement and prepare three steps and carry out, and preparation flow is as follows:
The first step:
Second step:
The 3rd step:
Preparation process major control condition:
(1) composite adhesive preparation: 120 ℃ of new cobalt decanoate fusion controlled temperature add cobalt boracylate 23 control intensification temperature to 180 ℃ formation homogeneous liquation in the time of 120 ℃; Homogeneous liquation cooling temperature normal temperature;
(2) bind the rubber master batch preparation: natural gum is plasticated in mill, plasticates roller Wen Wendu＜50 ℃ time 8-10 minute, broken-(down)rubber and composite adhesive and auxiliary agent in mill mixing time 15-20 minute, parked 16-24 hour roller Wen Wendu＜60 ℃, and it is standby to roll into the 4-6mm thin slice;
(3) rubber cement preparation: shear and bind rubber master batch particle≤1cm * 1cm, stir 50 rev/mins of the mixing speed that slurry is sheared dissolving slurrying, the dissolving terminal point is that 99% rubber cement filters by 200 eye mesh screens.
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